Diketopyrrolopyrrole polymers and small molecules

ABSTRACT

The present invention relates to polymers, comprising a repeating unit of the formula (I), and compounds of formula (II), wherein Y, Y 15 , Y 16  and Y 17  are independently of each other a group of formula (a) characterized in that the polymers and compounds comprise silicon-containing solubilizing side chains and their use as organic semiconductor in organic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics and photodiodes.

The present invention relates to polymers, comprising a repeating unit of the formula (I), and compounds of formula (II), wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group of formula R

characterized in that the polymers and compounds comprise silicon-containing solubilizing side chains and their use as organic semi-conductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics and photodiodes.

It is one object of the present invention to provide polymers and small molecules, which show high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability, when used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

Said object has been solved by polymers, comprising a repeating unit of the formula

wherein a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; R¹ and R² may be the same or different and are selected from a C₁-C₁₀₀alkyl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si), a C₂-C₁₀₀alkenyl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si), a C₃-C₁₀₀alkinyl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si), a C₃-C₁₂cycoalkyl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C—C₁₂cycloalkylene, or D^(Si), a C₆-C₂₄aryl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); a C₂-C₂₀heteroaryl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cydoalkyl, —COO—C₁-C₁₈alkyl which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or Es; and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si)

E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³ or —O—SiR¹⁶¹R¹⁶²R¹⁶³;

D^(Si) is —SiR¹⁶¹R¹⁶²—, —SiR¹⁶¹R¹⁶²(O—SiR¹⁶¹R¹⁶²)_(d)— or —O—SiR¹⁶¹R¹⁶²—; R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy; R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cydoalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy;

R¹⁶⁹, R¹⁷⁰ and R¹⁷¹ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—Si(CH₃)₃, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy;

R¹⁶⁷ and R¹⁶⁸ are independently of each other hydrogen, C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl;

d is an integer from 1 to 50; R³⁹ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl,

Ar¹ Ar^(1′)Ar² Ar^(2′) Ar³ and Ar^(3′) are independently of each other

such as, for example

such as, for example,

wherein X is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—, —C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R¹⁰⁴)—,

R³ and R^(3′) are independently of each other hydrogen, halogen, E^(Si), halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₁-C₂₅alkoxy; R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) are independently of each other hydrogen, halogen, E^(Si), halogenated C₁-C₂alkyl, cyano, C₁-C₂alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ and R^(9′) are independently of each other hydrogen, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; C₁-C₂₅alkyl substituted with one or more E^(Si), or C₇-C₂₅arylalkyl, or R⁷ and R^(7′), or R⁹ and R^(9′) are together ═CR¹⁰⁴R^(104′); R⁸ and R^(8′) are independently of each other hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₁-C₂₅alkyl substituted with one or more E^(Si), or C₇-C₂₅arylalkyl, R¹¹ and R^(11′) are independently of each other C₁-C₂₅alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅ arylalkyl, or ≡R¹³, wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)sily group; or Ar¹, Ar^(1′) Ar², Ar^(2′), Ar³ and Ar^(3′) are independently of each other

such as, for example

such as, for example,

wherein X^(1′) is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—, —C(R¹⁰⁸)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano, COOR¹⁰³, a C₁-C₂₅alkyl group, or C₆-C₂₄aryl or C₂-C₂₀heteroaryl; R¹⁰³ is C₁-C₂₅alkyl, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl; R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₁₈alkoxy, R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl; C₁-C₂₅alkyl; which may be interrupted by —O—, or —S—; or —COOR¹⁰³; R¹⁰³ is as defined above; R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted by D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁸ and R¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, wherein R¹¹⁰ and R¹¹¹ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or R¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, which optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl,

D is —CO—, —COO—, —S—, —O—, or —NR¹¹²,

E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, or halogen, G is E, or C₁-C₁₈alkyl, and R¹¹² and R¹¹³ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, R¹¹⁴ is C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or ≡R¹¹⁶, wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are independently of each other hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹²² and R¹²² are independently of each other hydrogen, C₆-C₁₈ aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl; with the proviso that at least one of the groups R¹, R², R³, R^(3′), R⁴, R^(4′), R⁵, R^(5′), R⁶, R^(6′), R⁷, R^(7′), R⁸, R⁸, R⁹ and R^(9′) contains a group E^(Si) and/or D^(Si). a and a′ are preferably different from 0.

Advantageously, the polymer of the present invention, or an organic semiconductor material, layer or component, comprising the polymer of the present invention, can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).

The polymers of this invention preferably have a weight average molecular weight of 4,000 Daltons or greater, especially 4,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000 and most preferably 10,000 to 100,000 Daltons. Molecular weights are determined according to high-temperature gel permeation chromatography (HT-GPC) using polystyrene standards. The polymers of this invention preferably have a polydispersity of 1.01 to 10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5. The polymers of the present invention are preferably conjugated.

The oligomers (small molecules) of the present invention preferably have a weight average molecular weight below 4,000 Daltons.

In an embodiment of the present invention the polymer is a polymer of formula

wherein n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.

R¹ and R² may be the same or different and are preferably selected from a C₁-C₁₀₀alkyl group, which can optionally be substituted one or more times with E^(Si), C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cydoalkyl, cyano, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or can optionally be interrupted by D^(Si), —O—, —S—, —COO— or —OCO—;

a C₂-C₁₀₀alkenyl group, which can optionally be substituted one or more times with E^(Si), C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cydoalkyl, cyano, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or can optionally be interrupted by D^(Si), —O—, —S—, —COO— or —OCO—; a C₃-C₁₀₀alkinyl group, which can optionally be substituted one or more times with E^(Si), C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cydoalkyl, cyano, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or can optionally be interrupted by D^(Si), —O—, —S—, —COO— or —OCO—; a C₆-C₁₂ cydoalkyl group, which can optionally be substituted one or more times with E^(Si), C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; and/or can optionally be interrupted by D^(Si), —O—, —S—, —COO— or —OCO—; a C₆-C₂₄aryl group which can optionally be substituted one or more times with E^(Si), C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cydoalkyl, cyano, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl; a C₂-C₂₀heteroaryl group, which can optionally be substituted one or more times with E^(Si), C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, cyano, C₆-C₂₄aryl, or C₂-C₂₀heteroaryl, —CO—C₁-C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl, and —COO—C₁-C₁₈alkyl.

More preferably R¹ and R² are selected from C₁-C₅₀alkyl, especially C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₁-C₅₀haloalkyl, especially C₁-C₂₅haloalkyl, which is substituted one or more times with Es and/or interrupted one or more times with D^(Si); C₇-C₂₅arylalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₂-C₅₀alkenyl, especially C₂-C₂₅alkenyl, which is substituted one or more times with Es and/or interrupted one or more times with D^(Si); C₂-C₅₀haloalkenyl, especially C₂-25haloalkenyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₅-C₁₂cycloalkyl; which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); phenyl, or naphthyl which are substituted one or more times with E^(Si).

Even more preferably R¹ and R² are C₁-C₂₅alkyl which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); especially C₁-C₂₅alkyl which is substituted one or more times with E^(Si), very especially C₁-C₈alkyl which is substituted one or more times with E^(Si).

Most preferably R¹ and R² are C₁-C₈alkyl which is substituted with E^(Si). R¹ and R² may be different, but are preferably the same.

E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³, or —O—SiR¹⁶¹R¹⁶²R¹⁶³, preferably —SiR¹⁶¹R¹⁶²R¹⁶³.

D^(Si) is —SiR¹⁶¹R¹⁶²—, —SiR¹⁶¹R¹⁶²—(O—SiR¹⁶¹R¹⁶²)_(d)—, or —O—SiR¹⁶¹R¹⁶²—, preferably —SiR¹⁶¹R¹⁶²—, or —SiR¹⁶¹R¹⁶²—(O—SiR¹⁶¹R¹⁶²)_(d)—.

R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy; preferably hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —O—(SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶ or phenyl; more preferably C₁-C₈alkyl, C₅-C₆cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶ or phenyl; most preferably C₁-C₈alkyl, C₁-C₈haloalkyl, especially C₁-C₈alkyl which is substituted one, or more times with fluorine atoms; —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶ or —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶.

R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶R¹⁷⁰)_(d)—R¹⁷¹, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy; preferably hydrogen, C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; more preferably C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; most preferably C₁-C₈alkyl, C₁-C₈haloalkyl, especially C₁-C₈alkyl which is substituted one or more times with fluorine atoms; —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹ or —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹.

R¹⁶⁹, R¹⁷⁰ and R¹⁷¹ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—Si(CH₃)₃, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C₁-C₂₅alkyl, halogen, cyano, or C₁-C₂₅alkoxy; preferably hydrogen, C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₁-C₂₅alkenyl, —O—Si(CH₃)₃, or phenyl; more preferably C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; most preferably C₁-C₈alkyl, C₁-C₈haloalkyl, especially C₁-C₈alkyl which is substituted one or more times with fluorine atoms; or —O—Si(CH₃)_(3.) d is an integer from 1 to 50, especially 1 to 40, very especially 1 to 30, preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, even more preferably 1 to 5 and most preferably 1 to 3. R¹⁶⁷ and R¹⁶⁸ are independently of each other hydrogen, C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, or phenyl; preferably C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, or phenyl; most preferably C₁-C₂₅alkyl.

In a particularly preferred embodiment E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³. R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₂₅alkyl, especially C₁-C₈alkyl; C₁-C₂haloalkyl, especially C₁-C₈haloalkyl, such as, for example, —CF₃, —(CH₂)₂CF₃, —(CH₂)₂(CF₂)₅CF₃ and —(CH₂)₂(CF₂)₆CF₃; C₂-C₂₅alkenyl, especially C₂-C₈alkenyl; C₃-C₁₂ cycloalkyl, especially C₅-C₆cydoalkyl, which might optionally be substituted with C₁-C₄alkyl; phenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, or —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶. In case of a group —O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, or phenyl. In case of a group —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶R¹⁶⁴ and R¹⁶⁵ are independently of each other C₁-C₈alkyl, R¹⁶⁶ is C₁-C₈alkyl, or phenyl and d is an integer of 2 to 5.

Examples of preferred groups E^(Si) are shown below:

(*-indicates the bond to the carbon atom, to which the silyl group or siloxanyl group is connected).

In a particularly preferred embodiment D^(Si) is —SiR¹⁶R¹⁶²—, wherein R¹⁶¹ and R¹⁶² are independently of each other C₁-C₂alkyl, especially C₁-C₈alkyl; C₁-C₂₅haloalkyl, especially C₁-C₈haloalkyl, such as, for example, —CF₃, —(CH₂)₂CF₃, —(CH₂)₂(CF₂)₅CF₃ and —(CH₂)₂(CF₂)₆CF₃; C₂-C₂₅alkenyl, especially C₂-C₈alkenyl; or phenyl.

In another particularly preferred embodiment D^(Si) is —SiR¹⁶¹R¹⁶² (O-SiR¹⁶¹R¹⁶²)_(d)—, wherein d is 2 to 5 and R¹⁶¹ and R¹⁶² are C₁-C₂₅alkyl, especially C₁-C₈alkyl.

Examples of preferred groups D^(Si) are shown below:

Preferably at least one of R¹ and R² comprise a group E^(Si) and/or D^(Si). R¹ and R² are preferably the same.

Chiral side chains, such as R¹ and R² can either be homochiral, or racemic, which can influence the morphology of the compounds.

Preferably Ar¹ and Ar^(1′) are independently of each other a group of formula XIa, XIb, XIc, XIe, XIf, XII, XIp, XIr, XIs, Xix, XIIf, XIIg, XIIa, XIIId, or XIIII; more preferably a group of formula XIa, XIb, XIe, XIf, XIr, Xix, or XIIIa, still more preferably a group of formula XIa, XIb, or XIf, most preferred a group of formula XIa, or XIf, especially XIa.

Preferably, R³ and R^(3′) are independently of each other hydrogen, halogen, E^(Si), CF₃, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₁-C₂₅alkoxy; more preferably CF₃, cyano or C₁-C₂₅alkyl; most preferred hydrogen, or C₁-C₂₅alkyl.;

Preferably, R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano or a C₁-C₂₅alkyl group, more preferably hydrogen, or a C₁-C₂₅alkyl group, most preferred hydrogen.

Preferably, R⁴, R^(4′), R⁵, R^(5′), R⁶ and R^(′) are independently of each other hydrogen, halogen, E^(Si), CF₃, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₁-C₂₅alkoxy, more preferably hydrogen, CF₃, cyano or C₁-C₂₅alkyl; most preferred hydrogen, or C₁-C₂₅alkyl.

Preferably R⁷, R^(7′), R⁹ and R^(9′) are independently of each other hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), more preferably C₄-C₂₅alkyl.

Preferably, R⁸ and R^(8′) are independently of each other hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl, more preferably hydrogen, or C₁-C₂₅alkyl.

Preferably, R¹¹ and R^(11′) are independently of each other a C₁-C₂₅alkyl group, especially a C₁-C₈alkyl group, or phenyl; more preferably a C₁-C₈alkyl group.

Preferably, R¹² and R^(12′) are independently of each other hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkoxy, or ≡R¹³, wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group, more preferably hydrogen, C₁-C₂₅alkyl, or C₁-C₂₅alkoxy.

If Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) are independently of each other a group of formula XVa to XVh, XVI, or XVII, groups of formula XVa, XVb, XVc, XVIa, XVIb, XVIIa, and XVIIb are preferred, groups of formula XVa, XVb, XVc, XVIa, and XVIb are more preferred. Among groups of formula XVa, XVb, XVc, XVIa, and XVIb, groups of formula XVa, and XVb are most preferred.

If Ar², Ar^(2′), Ar³, Ar^(3′), Ar⁴ and Ar^(4′) are independently of each other a group of formula XIa to XIz, XIIa to XIIk, or XIII, groups of formula XIa, XIb, XIc, XIe, XIf, XII, XIp, XIr, XIs, XIx, XIIf, XIIg, XIIIa, XIIId, and XIIII are preferred; groups of formula XIa, XIb, XIe, XIf, XIr, Xix, and XIIIa are more preferred, and groups of formula XIa, XIb, and XIf are still more preferred.

Most preferred is a group of formula XIa, or XIf, especially XIa.

Preferably, R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₁₈alkoxy, more preferably C₁-C₂₅alkyl or C₁-C₁₈alkoxy, most prefered hydrogen, or C₁-C₂₅alkyl.

R¹⁰⁷ is preferably hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl, more preferably hydrogen, or C₁-C₂₅alkyl, most preferred C₄-C₂₅alkyl.

Preferably, R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted by D, C₇-C₂₅arylalkyl, C₂-C₁₈alkenyl, or C₇-C₂₅aralkyl, or R¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, which optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, D is —CO—, —COO—, —S— or —O—, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN or halogen, G is E, or C₁-C₁₈alkyl. More preferably, R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl or C₇-C₂₅arylalkyl. Most preferred Rile and R¹⁰⁹ are independently of each other H, or C₁-C₂₅alkyl.

D is preferably —CO—, —COO—, —S— or —O—, more preferably —COO—, —S— or —O—, most preferred —S— or —O—.

Preferably, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, or halogen, more preferably C₁-C₈alkoxy, CN, or halogen, most preferred halogen, especially F.

Preferably, R¹¹² and R¹¹³ are independently of each other H; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, more preferably H, or C₁-C₁₈alkyl; most preferred C₁-C₁₈alkyl.

In a preferred embodiment the present invention is directed to polymers, comprising a repeating unit of the formula

wherein R¹ and R² may be the same or different and are selected from C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₁-C₂₅ haloalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₇-C₂₅arylalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₂-C₂₅alkenyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₂-C₂₅haloalkenyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₅-C₁₂cycloalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); phenyl, or naphthyl which are substituted one or more times with E^(Si); and a is 1, 2, or 3, a′ is 1, 2, or 3; wherein D^(Si), E^(Si), Ar¹ and Ar^(1′) are as defined above.

In said embodiment the following preferences apply with respect to the substituents:

R¹ and R² may be the same or different and are selected from C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si). R¹ and R² may be different, but are preferably the same. D^(Si) is preferably —SiR¹⁶¹R¹⁶²—, wherein R¹⁶¹ and R¹⁶² are independently of each other C₁-C₂₅alkyl, especially C₁-C₈alkyl; C₁-C₂₅haloalkyl, especially C₁-C₈haloalkyl, such as, for example, —CF₃, —(CH₂)₂CF₃, —(CH₂)₂(CF₂)₅CF₃ and —(CH₂)₂(CF₂)₆CF₃; C₂-25alkenyl, especially C₂-C₈alkenyl; or phenyl.

E^(Si) is preferably —SiR¹⁶¹R¹⁶²R¹⁶³. R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₂₅alkyl, especially C₁-C₈alkyl; C₁-C₂₅haloalkyl, especially C₁-C₈haloalkyl, such as, for example, —CF₃, —(CH₂)₂CF₃, —(CH₂)₂(CF₂)₅CF₃ and —(CH₂)₂(CF₂)₆CF₃; C₂-C₂₅alkenyl, especially C₂-C₈alkenyl; C₃-C₁₂cycloalkyl, especially C₅-C₆cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; phenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, or —(O—SiR⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶.

a and a′ may be different, but are preferably the same. a and a′ are preferably 1, or 2, more preferably 1.

Ar¹ and Ar^(1′) are preferably selected from groups of formula XIa to XIz, XIIa to XIIIk, XIII, especially XIIIa to XIIII, and XIV. Ar¹ and Ar^(1′) may be different, but are preferably the same. More preferably, Ar¹ and Ar^(1′) are independently of each a group of formula XIa, XIb, XIc, XIe, XIf, XII, XIp, XIr, XIs, XIx, XIIIf, XIIg, XIIIa, XIIId, or XIIII (as defined above).

Even more preferably, Ar¹ and Ar^(1′) are a group of formula XIa, XIb, XIe, XIf, XIr, XIx, or XIIIa. Still more preferably Ar¹ and Ar^(1′) are a group of formula XIa, XIb, or XIf. Most preferred Ar¹ and Ar^(1′) are a group of formula XIa, or XIf, especially XIa.

In a further preferred embodiment the present invention is directed to polymers, comprising a repeating unit of the formula

wherein R¹ and R² may be the same or different and are selected from C₁-C₈alkyl which is substituted with E^(Si),

E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³;

R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₈alkyl, C₅-C₆cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, or phenyl; R¹⁶⁴, R¹⁶⁵, R¹⁶⁶ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; R¹⁶⁹, R¹⁷⁰, R¹⁷¹ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; d is an integer from 1 to 10;

In said embodiment the following preferences apply with respect to the substituents:

R³ and R^(3′) are independently of each other hydrogen, or C₁-C₂₅alkyl; and R⁸ and R^(8′) are independently of each other hydrogen, or C₁-C₂₅alkyl.

Repeating) unit(s) of the formula (Ia), (Ib) and (Id) are preferred; repeating unit(s) of the formula (Ia) and (Id) are more preferred; repeating unit(s) of the formula (Ia) are most preferred.

In another embodiment the present invention is directed to polymers, comprising repeating units of the formula *A*and *COM¹*, wherein

A is a repeating unit of formula (I), and —COM¹- is a repeating unit, which has the meaning of Ar², wherein Ar² is as defined in claim 1, or is a group of formula *Ar¹⁴_(s)Ar¹⁵_(t)Ar¹⁶_(u)Ar¹⁷_(v)*, Ar¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ have independently of each other the meaning of Ar². Ar¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ are preferably independently of each other a group of formula

wherein one of X⁵ and X⁶ is N and the other is CR¹⁴, and R¹⁴, R^(14′), R¹⁷ and R^(17′) are independently of each other H, or a C₁-C₂₅alkyl group.

Examples of repeating units —COM¹- are groups of formula XIa, XIb, XIc, XIe, XIf, XII, XIp, XIr, XIs, Xix, XIIf, XIIg, XIIIa, XIIId, XIIII, XVa, XVb, XVc, XVIa, XVIb, XVIIa, or XVIIb. Among these groups groups of formula XIa, XIb, XIe, XIf, XIr, XIx, XIIIa, XVa, XVb, XVc, XVIa, or XVIb are preferred, groups of formula XIa, XIb, XIf, XVa, or XVb are more preferred, groups of formula XIa, XIf, or XVa are still more preferred. Groups of formula XIa are most preferred.

Examples of a group of formula *Ar¹⁴_(k)Ar¹⁵_(l)Ar¹⁶_(r)Ar¹⁷_(z)* are

If substituents, such as, for example, R¹⁴ and R^(14′), appear more than one time in a formula they can be the same, or different.

In a particularly preferred embodiment the repeating unit —COM¹- is a group of formula

where R³, R^(3′), R¹⁴ and R^(14′) are independently of each other hydrogen, or C₁-C₂₅alkyl, and R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano or a C₁-C₂₅alkyl group.

In a preferred embodiment of the present invention the polymer is a copolymer, comprising repeating units of formula *ACOM¹-* (VII), especially a copolymer of formula, wherein A and COM¹ are as defined above; n is a number which results in a molecular weight of 4,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000 and most preferably 10,000 to 100,000 Daltons. n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.

In a preferred embodiment the present invention is directed to polymers, wherein A is a repeating unit of formula (Ia), or (Id), (as defined above) and *COM¹* is a group of formula

where R³, R^(3′), R¹⁴ and R^(14′) are independently of each other hydrogen, or C₁-C₂₅alkyl, and R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano or a C₁-C₂₅alkyl group.

In a preferred embodiment the present invention is directed to copolymers, wherein *A* is RF is

and *COM¹* is Ar²—, or —Ar²—Ar³—; especially Ar²—, or —Ar¹⁴—Ar¹⁵—; very especially —Ar²—. *A* is preferably

Among the polymers of formula I the following polymers are preferred:

wherein n is 4 to 1000, R¹ and R² may be the same or different and are selected from C₁-C₈alkyl which is substituted with E^(Si), R³ and R^(3′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy;

E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³;

R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₈alkyl, C₅-C₆cycloalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, or phenyl; R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl;

R¹⁶⁹, R¹⁷⁰ and R¹⁷¹ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl;

d is an integer from 1 to 10; R^(3″) and R^(3*) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy; R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano, COOR¹⁰³, or C₁-C₂₅alkyl, especially hydrogen, cyano, or COOR¹⁰³, wherein R¹⁰³ is C₁-C₈alkyl; and R¹⁰⁵ and R^(105′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy, especially especially hydrogen, cyano, or C₁-C₂₅alkyl.

Examples of particular preferred polymers are shown below:

wherein n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.

The polymers of the present invention can comprise more than 2 different repeating units, such as, for example, repeating units A, B and D, which are different from each other. If the polymers comprise repeating units of the formula *A-D* and *B-D* , they are preferably (random) copolymers of formula *A-D*_(x)-*B-D_(y)* , wherein x=0.995 to 0.005, y=0.005 to 0.995, especially x=0.2 to 0.8, y=0.8 to 0.2, and wherein x+y=1. A is a repeating unit of formula (I), D* is a repeating unit —COM¹- and B is a repeating unit —COM¹-, or a repeating unit of formula (I); with the proviso that A, B and D* are different from each other.

Copolymers of formula VII can be obtained, for example, by the Suzuki reaction. The condensation reaction of an aromatic boronate and a halogenide, especially a bromide, commonly referred to as the “Suzuki reaction”, is tolerant of the presence of a variety of organic functional groups as reported by N. Miyaura and A. Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 (1995). Preferred catalysts are 2-dicyclohexylphosphino-2′,6′-dialkoxybiphenyl/palladium(II)acetates, tri-alykl-phosphonium salts/palladium (0) derivatives and tri-alkylphosphine/palladium (0) derivatives. Especially preferred catalysts are 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl (sPhos)/palladium(II)acetate and, tri-tertbutylphosphonium tetrafluoroborate ((t-Bu)₃P*HBF₄)/tris(dibenzylideneacetone) dipalladium (0) (Pd₂(dba)₃) and tri-tert-butyiphosphine (t-Bu)₃P/tris(dibenzylideneacetone) dipalladium (0) (Pd₂(dba)₃). This reaction can be applied to preparing high molecular weight polymers and copolymers.

To prepare polymers corresponding to formula VII a dihalogenide of formula X¹⁰-A-X¹⁰ is reacted with an (equimolar) amount of a diboronic acid or diboronate corresponding to formula X¹¹COM¹X¹¹; or a dihalogenide of formula X¹⁰COM¹X¹⁰ is reacted with an (equimolar) amount of a diboronic acid or diboronate corresponding to formula X¹¹-A-X¹¹, wherein X¹⁰ is halogen, especially Br, and X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group and Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—Cy¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or a C₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or —C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkyl group, under the catalytic action of Pd and triphenylphosphine. The reaction is typically conducted at about 0° C. to 180° C. in an aromatic hydrocarbon solvent such as toluene, xylene. Other solvents such as dimethytformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon. An aqueous base, preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scavenger. A polymerization reaction may take 0.2 to 100 hours. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Controll of molecular weight is possible by using either an excess of dibromide, diboronic acid, or diboronate, or a chain terminator.

According to the process described in WO2010/136352 the polymerisation is carried out in presence of

a) a catalyst/ligand system comprising a palladium catalyst and an organic phosphine or phosphonium compound, b) a base, c) a solvent or a mixture of solvents, characterized in that the organic phosphine is a trisubstituted phosphine of formula

or phosphonium salt thereof, wherein X″ independently of Y″ represents a nitrogen atom or a C—R²″ group and Y″ independently of X″ represents a nitrogen atom or a C—R⁹″ group, R¹″ for each of the two R¹″ groups independently of the other represents a radical selected from the group C₁-C₂₄-alkyl, C₃-C₂₀-cycloalkyl, which includes especially both monocyclic and also bi- and tri-cyclic cycloalkyl radicals, C₅-C₁₄-aryl, which includes especially the phenyl, naphthyl, fluorenyl radical, C₂-C₁₃-heteroaryl, wherein the number of hetero atoms, selected from the group N, O, S, may be from 1 to 2, wherein the two radicals R^(1″) may also be linked to one another, and wherein the above-mentioned radicals R^(1″) may themselves each be mono- or poly-substituted independently of one another by substituents selected from the group hydrogen, C₁-C₂₀-alkyl, C₂-20-alkenyl, C₃-C₈-cydoalkyl, C₂-C₉-hetero-alkyl, C₅-C₁₀-aryl, C₂-C₉-heteroaryl, wherein the number of hetero atoms from the group N, O, S may be from 1 to 4, C₁-C₂₀-alkoxy, C₁-C₁₀-haloalkyl, hydroxy, amino of the forms NH—(C₁-C₂₀-alkyl), NH—(C₅-C₁₀-aryl), N(C₁-C₂₀-alkyl)₂, N(C₁-C₂₀-alkyl) (C₅-C₁₀-aryl), N(C₅-C₁₀-aryl)₂, N(C₁-C₂₀-alky/C₅-C₁₀-aryl₃)₃ ⁺, NH—CO—C₁-C₂₀-alkyl, NH—CO—C₅-C₁₀-aryl, carboxylato of the forms COOH and COOQ (wherein Q represents either a monovalent cation or C₁-C₈-alkyl), C₁-C₆-acyloxy, sulfinato, sulfonato of the forms SO₃H and SO₃Q′ (wherein Q′ represents either a monovalent cation, C₁-C₂₀-alkyl, or C₅-C₁₀-aryl), tri-C₁-C₆-alkylsilyl, wherein two of the mentioned substituents may also be bridged with one another, R²″-R⁹″represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH— alkyl, N-(alkyl)₂, O-(aryl), NH-(aryl), N-(alkyl)(aryl), O—CO-alkyl, O—CO-aryl, F, Si(alkyl)₃, CF₃, CN, CO₂H, COH, SO₃H, CONH₂, CONH(alkyl), CON(alkyl)₂, SO₂(alkyl), SO(alkyl), SO(aryl), SO₂(aryl), SO₃(alkyl), SO₃(aryl), S-alkyl, S-aryl, NH—CO(alkyl), CO₂(alkyl), CONH₂, CO(alkyl), NHCOH, NHCO₂(alkyl), CO(aryl), CO₂(aryl) radical, wherein two or more adjacent radicals, each independently of the other (s), may also be linked to one another so that a condensed ring system is present and wherein in R^(2″) to R^(9″) alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms which may in each case be linear or branched, alkenyl represents a mono- or poly- unsaturated hydrocarbon radical having from 2 to 20 carbon atoms which may in each case be linear or branched, cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms, aryl represents a 5- to 14-membered aromatic radical, wherein from one to four carbon atoms in the aryl radical may also be replaced by hetero atoms from the group nitrogen, oxygen and sulfur so that a 5- to 14-membered heteroaromatic radical is present, wherein the radicals R^(2″) to R^(9″) may also carry further substituents as defined for R^(1″).

The organic phosphines and their synthesis are described in WO2004101581.

Preferred organic phosphines are selected from trisubstituted phosphines of formula

Cpd. R^(1″) R5^(″) R^(6″) R^(3″) R^(4″) A-1

H H H H A-2 cyclohexyl H H H H A-3 phenyl H H H H A-4 adamantyl H H H H A-5 cyclohexyl —OCH₃ H H H A-6 cyclohexyl ¹⁾ ¹⁾ H H A-7

¹⁾ ¹⁾ H H A-8 phenyl ¹⁾ ¹⁾ H H A-9 adamantyl ¹⁾ ¹⁾ H H  A-10 cyclohexyl H H ²⁾ ²⁾  A-11

H H ²⁾ ²⁾  A-12 phenyl H H ²⁾ ²⁾  A-13 adamantyl H H ²⁾ ²⁾

Examples of preferred catalysts include the following compounds:

palladium(II) acetylacetonate, palladium(0) dibenzylidene-acetone complexes, palladium(II) propionate, Pd₂(dba)₃: [tris(dibenzylideneacetone) dipalladium(0)], Pd(dba)₂: [bis(dibenzylideneacetone) palladium(0)], Pd(PR₃)₂, wherein PR₃ is a trisubstituted phosphine of formula VI, Pd(OAc)₂: [palladium(II) acetate], palladium(II) chloride, palladium(II) bromide, lithium tetrachloropalladate(II), PdCl₂(PR₃)₂; wherein PR₃ is a trisubstituted phosphine of formula VI; palladium(0) diallyl ether complexes, palladium(II) nitrate, PdCl₂(PhCN)₂: [dichlorobis(benzonitrile) palladium(II)], PdCl₂(CH₃CN): [dichlorobis(acetonitrile) palladium(II)], and PdCl₂(COD): [dichloro(1,5-cyclooctadiene) palladium(II)].

Especially preferred are PdCl₂, Pd₂(dba)₃, Pd(dba)₂, Pd(OAc)₂, or Pd(PR₃)₂. Most preferred are Pd₂(dba)₃ and Pd(OAc)_(2.)

The palladium catalyst is present in the reaction mixture in catalytic amounts. The term “catalytic amount” refers to an amount that is dearly below one equivalent of the (hetero)aromatic compound(s), preferably 0.001 to 5 mol-%, most preferably 0.001 to 1 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used.

The amount of phosphines or phosphonium salts in the reaction mixture is preferably from 0.001 to 10 mol-%, most preferably 0.01 to 5 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The preferred ratio of Pd:phosphine is 1:4.

The base can be selected from all aqueous and nonaqueous bases and can be inorganic, or organic. It is preferable that at least 1.5 equivalents of said base per functional boron group is present in the reaction mixture. Suitable bases are, for example, alkali and alkaline earth metal hydroxides, carboxylates, carbonates, fluorides and phosphates such as sodium and potassium hydroxide, acetate, carbonate, fluoride and phosphate or also metal alcoholates. It is also possible to use a mixture of bases. The base is preferably a lithium salt, such as, for example, lithium alkoxides (such as, for example, lithium methoxide and lithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluoride and/or phosphate.

The at present most preferred base is aqueous LiOHxH₂O (monohydrate of LiOH) and (waterfree) LiOH.

The reaction is typically conducted at about 0° C. to 180° C., preferably from 20 to 160° C., more preferably from 40 to 140° C. and most preferably from 40 to 120° C. A polymerization reaction may take 0.1, especially 0.2 to 100 hours.

In a preferred embodiment of the present invention the solvent is THF, the base is LiOH*H₂O and the reaction is conducted at reflux temperature of THF (about 65° C.).

The solvent is for example selected from toluene, xylenes, anisole, THF, 2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene or solvent mixtures comprising one or more solvents like e.g. THF/toluene and optionally water. Most preferred is THF, or THF/water.

Advantageously, the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃, (tris(dibenzylideneacetone)dipalladium(0)) and an organic phosphine A-1 to A-13,

b) LiOH, or LiOHxH₂O; and

c) THF, and optionally water. If the monohydrate of LiOH is used, no water needs to be added.

Most preferred the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃ (tris(dibenzylideneacetone)dipalladium(0)) and

b) LiOHxH₂O; and

c) THF. The palladium catalyst is present in an amount of preferably about 0.5 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The amount of phosphines or phosphonium salts in the reaction mixture is preferably about 2 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The preferred ratio of Pd:phosphine is about 1:4.

Preferably the polymerization reaction is conducted under inert conditions in the absence of oxygen. Nitrogen and more preferably argon are used as inert gases.

The process described in WO2010/136352 is suitable for large-scale applications, is readily accessible and convert starting materials to the respective polymers in high yield, with high purity and high selectivity. The process can provide polymers having weight average molecular weights of at least 10,000, more preferably at least 20,000, most preferably at least 30,000. The at present most preferred polymers have a weight average molecular weight of 30,000 to 80,000 Daltons. Molecular weights are determined according to high-temperature gel permeation chromatography (HT-GPC) using polystyrene standards. The polymers preferably have a polydispersibility of 1.01 to 10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5.

If desired, a monofunctional aryl halide or aryl boronate, such as, for example,

may be used as a chain-terminator in such reactions, which will result in the formation of a terminal aryl group.

It is possible to control the sequencing of the monomeric units in the resulting copolymer by controlling the order and composition of monomer feeds in the Suzuki reaction.

The polymers of the present invention can also be sythesized by the Stille coupling (see, for example, Babudn et al, J. Mater. Chem., 2004, 14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). To prepare polymers corresponding to formula VII a dihalogenide of formula X¹⁰-A-X¹⁰ is reacted with a compound of formula X^(11′)—COM¹-X^(11′), or a dihalogenide of formula X¹⁰—COM¹-X¹⁰ is reacted with a compound of formula X^(11′)-A-X^(11′), wherein X^(11′) is a group —SnR²⁰⁷R²⁰⁸R²⁰⁹ and X¹⁰ is as defined above, in an inert solvent at a temperature in range from 0° C. to 200° C. in the presence of a palladium-containing catalyst, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein two groupss optionally form a common ring and these radicals are branched or unbranched. It must be ensured here that the totality of all monomers used has a highly balanced ratio of organotin functions to halogen functions. In addition, it may prove advantageous to remove any excess reactive groups at the end of the reaction by end-capping with monofunctional reagents. In order to carry out the process, the tin compounds and the halogen compounds are preferably introduced into one or more inert organic solvents and stirred at a temperature of from 0 to 200° C., preferably from 30 to 170° C. for a period of from 1 hour to 200 hours, preferably from 5 hours to 150 hours. The crude product can be purified by methods known to the person skilled in the art and appropriate for the respective polymer, for example repeated re-precipitation or even by dialysis.

Suitable organic solvents for the process described are, for example, ethers, for example diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether, hydrocarbons, for example hexane, isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols, for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and tertbutanol, ketones, for example acetone, ethyl methyl ketone and isobutyl methyl ketone, amides, for example dimethytformamide (DMF), dimethylacetamide and N-methylpyrrolidone, nitriles, for example acetonitrile, propionitrile and butyronitrile, and mixtures thereof.

The palladium and phosphine components should be selected analogously to the description for the Suzuki variant.

The Stille coupling reaction is preferred over the Suzuki coupling reaction, if the silyl groups E^(Si) or D^(Si) might hydrolyze under the Suzuki reaction conditions.

Alternatively, the polymers of the present invention can also be synthesized by the Negishi reaction using a zinc reagent A-(ZnX¹²)₂, wherein X¹² is halogen and halides, and COM¹-(X²³)₂, wherein X²³ is halogen or trifiate, or using A-(X²³)₂ and COM¹-(ZnX¹²)₂. Reference is, for example, made to E. Negishi et al., Heterocycles 18 (1982) 117-22.

Alternatively, the polymers of the present invention can also be synthesized by the Hiyama reaction using a organosilicon reagent A-(SiR²¹OR²¹¹R²¹²)₂, wherein R²¹⁰, R²¹¹ and R²¹² are identical or different and are halogen, or C₁-C₆alkyl, and COM¹-(X²³)₂, wherein X²³ is halogen or triflate, or using A-(X²³)₂ and COM¹-(SiR²¹⁰R²¹¹R²¹²)₂. Reference is, for example, made to T. Hiyama et al., Pure Appl. Chem. 66 (1994) 1471-1478 and T. Hiyama et al., Synlett (1991) 845-853.

Homopolymers of the type (A)_(n) can be obtained via Yamamoto coupling of dihalides X¹⁰-A-X¹⁰, where X¹⁰ is halogen, preferably bromide. Alternatively homopolymers of the type (A)_(n) can be obtained via oxidative polymerization of units X¹⁰A-X¹⁰, where X¹⁰ is hydrogen, e.g. with FeCl₃ as oxidizing agent.

In case of R¹ and R²C₁-C₂₅alky-SiR¹⁶¹R¹⁶²R¹⁶³ groups may be obtained by first alkylating the nitrogen atoms of the DPP with a C₂-C₂₅iodoalkenyl group and then the addition of an H—Si bond across a double bond by hydrosilation. Advantageously, platinum(II) compounds such as Karstedt catalyst, platinum chloride olefin complex and [PtCI₂(cycooctadiene)] are used as catalyst. Karstedt catalyst is a compound of platinum(0) and divinyttetramethyldisiloxane.

The compounds of the formula

are intermediates in the production of the polymers of the present invention, are new and form a further subject of the present invention. R¹, R², a, a′, b , b′, c, c′, Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are as defined above, and X² and X^(2′) are independently of each other halogen, ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein two groups optionally form a common ring and these groups are branched or unbranched and X¹² is a halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group and Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or a C₁-C₁₀alkyl group, and Y¹³ and Y¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkyl group. X² and X^(2′) are preferably the same. With respect to the substituents R¹, R², a, a′, b, b′, c, c′, Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) the same preferences apply as for the compounds of formula I.

Examples of compounds of formula V are shown below:

wherein X² is as defined above. R¹ and R² may be the same or different and are preferably selected from C₁-C₈alkyl which is substituted with E^(Si). R³ and R^(3′) are independently of each other hydrogen or C₁-C₂₅alkyl. R⁸ and R^(8′) are independently of each other hydrogen or C₁-C₂₅alkyl, especially C₁-C₂₅alkyl.

Among the compounds of formula V the following compounds are preferred:

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₁₀₀alkyl is preferably C₁-C₃₈alkyl, especially C₁-C₂₅alkyl. C—C₂₅alkyl (C₁-C₁₈alkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl. C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl.

C₂-C₁₀₀alkenyl is preferably C₂-C₂alkenyl. C₂-C₂alkenyl (C₂-C₁₈alkenyl) groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₃-C₁₀₀alkinyl is preferably C₂-C₂₅alkinyl. C₂₋₂₅alkinyl (C₂₋₁₈alkinyl) is straight-chain or branched and preferably C₂₋₈-alkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthio groups as exemplified further below. The term “aliphatic group” comprises also alkyl groups wherein certain non-adjacent carbon atoms are replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group can be regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

An aliphatic hydrocarbon group having up to 25 carbon atoms is a linear or branched alkyl, alkenyl or alkynyl (also spelled alkinyl) group having up to 25 carbon atoms as exemplified above.

Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) free valencies, e.g. trimethylene or tetramethylene.

Alkenylene is bivalent alkenyl, i.e. alkenyl having two (instead of one) free valencies, e.g. —CH₂—CH═CH—CH₂—.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkythio groups as exemplified further below. The term “aliphatic group” comprises also alkyl groups wherein certain non-adjacent carbon atoms are replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group can be regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

A cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl group which may be substituted by one or more aliphatic and/or cydoaliphatic hydrocarbon groups.

A cycloaliphatic-aliphatic group is an aliphatic group substituted by a cycloaliphatic group, wherein the terms “cycloaliphatic” and “aliphatic” have the meanings given herein and wherein the free valency extends from the aliphatic moiety. Hence, a cydoaliphaticaliphatic group is for example a cycloalkyl-alkyl group.

A “cycloalkenyl group” means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cydohexenyl and the like, which may be unsubstituted or substituted by one or more aliphatic and/or cycloaliphatic hydrocarbon groups and/or condensed with phenyl groups.

A bivalent group of the formula IVb wherein R²⁸ and R²⁷ together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, is e.g. a group of the formula

wherein A²⁰ represents linear or branched alkylene having up to 25 carbon atoms, preferably ethylene or propylene which may be substituted by one or more alkyl groups, and Y²⁰ represents oxygen or sulphur. For example, the bivalent group of the formula —Y²⁰-A²⁰-O— represents —O—CH₂—CH₂—O— or —O—CH₂—CH₂—CH₂—O—.

A group of the formula IVa wherein two groups R²² to R²⁶ which are in the neighborhood of each other, together represent alkylene or alkenylene having up to 8 carbon atoms, thereby forming a ring, is e.g. a group of the formula

(XXXII), or (XXXIII) wherein in the group of the formula XXXII R²³ and R²⁴ together represent 1,4-butylene and in the group of the formula XXXIII R²³ and R²⁴ together represent 1,4-but-2-en-ylene.

C₁-C₂₅alkoxy groups (C₁-C₁₈alkoxy groups) are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of C₁-C₈alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁-C₄alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthio group” means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulfur atom.

C₁-C₁₈perfluoroalkyl, especially C₁-C₄perfluoroalkyl, is a branched or unbranched radical such as for example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

C₁-C₂₅haloalkyl means a C₁-C₂₅alkyl group which is substituted with one or more halogen atoms.

The term “carbamoyl group” is typically a C₁₋₁₈carbamoyl radical, preferably C₁₋₈carbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

A cycloalkyl group is typically C₃-C₁₂cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, cydooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted. The cycloalkyl group, in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen and cyano. Examples of such condensed cydohexyl groups are:

in particular

wherein R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵ and R¹⁵⁶ are independently of each other C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particular hydrogen.

A cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkyl group, e.g. cyclohexyl-methyl.

C₆-C₂₄aryl (C₆-C₁₈aryl) is typically phenyl, indenyl, azulenyl, naphthyl, biphenyl, asindacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted. Examples of C₆-C₁₂aryl are phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthryl, which may be unsubstituted or substituted.

C₇-C₂₅aralkyl is typically benzyl, 2-benzyl-2-propyl, B-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2-phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

Heteroaryl is typically C₂-C₂₀heteroaryl, i.e. a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic group with five to 30 atoms having at least six conjugated n-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted or substituted.

C₆-C₂₄arylen groups, which optionally can be substituted, are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene, or 2-naphthylene and biphenylylene.

Preferred C₂-C₂₀heteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolylene, dibenzofuranylene which optionally can be substituted.

Examples of C₃-C₁₂ cycloalkylene are cyclopropylene, cyclopentylene, cyclohexylene. Possible substituents of the above-mentioned groups are C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, a carbamoyl group, a nitro group or a silyl group, especially C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, or a cyano group.

C₁-C₁₈alkyl interrupted by one or more O is, for example, (CH₂CH₂O)₁₋₉R^(x), where Rx is H or C₁-C₁₀alkyl, CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y′) is C₁-C₁₈alkyl, and R^(y′) embraces the same definitions as R^(y) or is H.

If a substituent, such as, for example R³, occurs more than one time in a group, it can be different in each occurrence.

A mixture containing a polymer of the present invention results in a semi-conducting layer comprising a polymer of the present invention (typically 5% to 99.9999% by weight, especially 20 to 85% by weight) and at least another material. The other material can be, but is not restricted to a fraction of the same polymer of the present invention with different molecular weight, another polymer of the present invention, a semi-conducting polymer, organic small molecules, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles (Au, Ag etc.), insulator materials like the ones described for the gate dielectric (PET, PS etc.). The polymers of the present invention can be blended with compounds of formula III according to the present invention, or small molecules described, for example, in WO2009/047104, WO2010108873 (PCT/EP2010/053655), WO009/047104, U.S. Pat. No. 6,690,029, WO2007082584, and WO2008107089:

WO2007082584:

WO2008107089

wherein one of Y^(1′) and Y^(2′) denotes —CH═ or ═CH— and the other denotes —X*—, one of Y^(3′) and Y^(4′) denotes —CH═ or ═CH— and the other denotes —X*—,

X* is —O—, —S—, —Se— or —NR′″—,

R* is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms, or aryl having 2-30 C-atoms, all of which are optionally fluorinated or perfluorinated, R′ is H, F, Cl, Br, I, CN, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms and optionally being fluorinated or perfluorinated, optionally fluorinated or perfluorinated aryl having 6 to 30 C-atoms, or CO₂R″, with R″ being H, optionally fluorinated alkyl having 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30 C-atoms, R′″ is H or cyclic, straight-chain or branched alkyl with 1 to 10 C-atoms, y is 0, or 1, x is 0, or 1

The polymer can contain a small molecule, or a mixture of two, or more small molecule compounds.

Accordingly, the present invention also relates to an organic semiconductor material, layer or component, comprising a polymer according to the present invention.

The polymers of the invention can be used as the semiconductor layer in semiconductor devices. Accordingly, the present invention also relates to semiconductor devices, comprising a polymer of the present invention, or an organic semiconductor material, layer or component. The semiconductor device is especially an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor.

The polymers of the invention can be used alone or in combination as the organic semiconductor layer of the semiconductor device. The layer can be provided by any useful means, such as, for example, vapor deposition (for materials with relatively low molecular weight) and printing techniques. The compounds of the invention may be sufficiently soluble in organic solvents and can be solution deposited and patterned (for example, by spin coating, dip coating, ink jet printing, gravure printing, fiexo printing, offset printing, screen printing, microcontact (wave)-printing, drop or zone casting, or other known techniques).

The polymers of the invention can be used in integrated circuits comprising a plurality of OTFTs, as well as in various electronic articles. Such articles include, for example, radio-frequency identification (RFID) tags, backplanes for flexible displays (for use in, for example, personal computers, cell phones, or handheld devices), smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-, mechanical- or temperature sensors), especially photodiodes, or security devices and the like.

A further aspect of the present invention is an organic semiconductor material, layer or component comprising one or more polymers of the present invention. A further aspect is the use of the polymers or materials of the present invention in an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET). A further aspect is an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET) comprising a polymer or material of the present invention.

The polymers of the present invention are typically used as organic semiconductors in form of thin organic layers or films, preferably less than 30 microns thick. Typically the semiconducting layer of the present invention is at most 1 micron (=1 μm) thick, although it may be thicker if required. For various electronic device applications, the thickness may also be less than about 1 micron thick. For example, for use in an OFET the layer thickness may typically be 100 nm or less. The exact thickness of the layer will depend, for example, upon the requirements of the electronic device in which the layer is used.

For example, the active semiconductor channel between the drain and source in an OFET may comprise a layer of the present invention.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,     -   a drain electrode,     -   a gate electrode,     -   a semiconducting layer,     -   one or more gate insulator layers, and     -   optionally a substrate, wherein the semiconductor layer         comprises one or more polymers of the present invention.

The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a polymer of the present invention located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.

The OFET device can be a top gate device or a bottom gate device.

Suitable structures and manufacturing methods of an OFET device are known to the person skilled in the art and are described in the literature, for example in WO03/052841.

The gate insulator layer may comprise for example a fluoropolymer, like e.g. the commercially available Cytop 809M@, or Cytop 107M@(from Asahi Glass). Preferably the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380). Other suitable fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont), or Fluoropel® (from Cytonix) or the perfluorosolvent FC 43@(Acros, No. 12377).

The semiconducting layer comprising a polymer of the present invention may additionally comprise at least another material. The other material can be, but is not restricted to another polymer of the present invention, a semi-conducting polymer, a polymeric binder, organic small molecules different from a polymer of the present invention, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles (Au, Ag etc.), and insulator materials like the ones described for the gate dielectric (PET, PS etc.). As stated above, the semiconductive layer can also be composed of a mixture of one or more polymers of the present invention and a polymeric binder. The ratio of the polymers of the present invention to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA). With this technique, a degradation of the electrical performance can be avoided (cf. WO2008/001123A1).

The polymers of the present invention are advantageously used in organic photovoltaic (PV) devices (solar cells). Accordingly, the invention provides PV devices comprising a polymer according to the present invention. A device of this construction will also have rectifying properties so may also be termed a photodiode. Photoresponsive devices have application as solar cells which generate electricity from light and as photodetectors which measure or detect light.

The PV device comprise in this order:

(a) a cathode (electrode), (b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (c) a photoactive layer, (d) optionally a smoothing layer, (e) an anode (electrode), (f) a substrate.

The photoactive layer comprises the polymers of the present invention. Preferably, the photoactive layer is made of a conjugated polymer of the present invention, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor. As stated above, the photoactive layer may also contain a polymeric binder. The ratio of the polymers of formula I to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA).

For heterojunction solar cells the active layer comprises preferably a mixture of a polymer of the present invention and a fullerene, such as [60]PCBM (=6,6-phenyl-C₆₁-butyric acid methyl ester), or [70]PCBM, in a weight ratio of 1:1 to 1:3. The fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C₆₀) and the related “spherical” fullerenes as well as carbon nanotubes. Fullerenes may be selected from those known in the art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₀ to C₉₆. Most preferably the fullerene is C₆₀ or C₇₀, such as [60]PCBM, or [70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics. The acceptor material can also be a material selected from the group consisting of any semi-conducting polymer, such as, for example, a polymer of the present invention, provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a polymer of the present invention as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-Blodgett (“LB”) method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer. Instead of toluene, which is typical, a dispersion agent such as chlorobenzene is preferably used as a solvent. Among these methods, the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, the casting method and ink jet printing method, the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyttetrahydrofurane, N,N-dimethytformamide, acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum. Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006) and WO2004/112161.

A so called tandem solar cell′ comprise in this order:

(a) a cathode (electrode), (b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (c) a photoactive layer, (d) optionally a smoothing layer, (e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.) (f) optionally an extra electrode to match the energy level, (g) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (h) a photoactive layer, (i) optionally a smoothing layer, (j) an anode (electrode), (k) a substrate.

The PV device can also be processed on a fiber as described, for example, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or films comprising the polymers of the present invention can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US2003/0021913.

It is another object of the present invention to provide compounds, which show high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability, when used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

In a further embodiment the present invention relates to compounds of the formula A¹-YA³-Y¹⁵_(o)A⁴-Y¹⁶_(p)A⁵-Y¹⁷_(q)A² (III), wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group of formula

o is 0, or 1, p is 0, or 1, q is 0, or 1;

A¹ and A² are independently of each other a group of formula Ar¹_(a)Ar²_(b)Ar³_(c)—R¹⁰,

A³, A⁴ and A⁵ are independently of each other a group of formula *Ar⁴_(k)Ar⁵_(l)Ar⁶_(r)Ar⁷_(z)* k is 0, 1, 2, or 3; 1 is 1, 2, or 3; r is 0, 1, 2,or 3; z is 0, 1, 2,or 3;

R¹⁰ is hydrogen, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted one or more times by E and/or interrupted one or more times by D, E^(Si), C₁-C₂₅alkyl which is substituted one or more times by E^(Si) and/or interrupted one or more times by D^(Si),

COO—C₁-C₁₈alkyl, C₄-C₁₈cycloalkyl group, C₄-C₁₈cycloalkyl group, which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈thioalkoxy, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl, which is substituted by G, or a group of formulae Iva to Ivm,

wherein R²² to R²⁶ and R²⁹ to R⁵⁸ represent independently of each other H, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, a C₄-C₁₈cycloalkyl group, a C₄-C₁₈cycloalkyl group, which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl, which is substituted by G, R²⁷ and R²⁸ are independently of each other hydrogen, C₁-C₂₅alkyl, halogen, cyano or C₇-C₂₅aralkyl, or R²⁷ and R²⁸ together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, R⁵⁹ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,

D is —CO—, —COO—, —S—, —O—, or —NR¹¹²—,

E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, or halogen, G is E, or C₁-C₁₈alkyl, and R¹¹² and R¹¹³ are independently of each other H; C₆-C₁₈ aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; R¹⁷² is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₁-C₂₅arylalkyl; R²¹⁴ and R²¹5 are independently of each other hydrogen, C₁-C₁₈alkyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CN or COOR²¹⁶; R²¹⁶ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl or C₂-C₂₀heteroaryl; Ar⁴, Ar⁵, Ar⁶ and Ar⁷ have independently of each other the meaning of Ar¹, and a, b, c, Ar¹, Ar², Ar³, R¹ and R² are as defined in claim 1; with the proviso that at least one of the groups R¹, R², R³, R^(3′), R⁴, R^(4′), R⁵, R^(5′), R⁶, R^(6′), R⁷, R^(7′), R⁸, R^(8′), R⁹ and R^(9′) contains a group E^(Si) and/or D^(Si).

Preferably, at least one of the groups R¹ and R² contains a group E^(Si) and/or D^(Si). More preferred, the groups R¹ and R² contain a group E^(Si) and/or D^(Si).

Among the compounds of the formula III compounds of formula

wherein R¹, R², A¹, A², A³, A⁴ and A⁵ are as defined above, R¹, R^(2′), R^(1″), R^(2″), R^(1*), R^(2*) have independently of each other the meaning of R¹; with the proviso that at least one of the groups R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) is a C₁-C₈alkyl group which is substituted with E^(Si), and

E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³;

R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₈alkyl, C₅-C₆cycoalkyl, which might optionally be substituted with C₁-C₄alkyl; C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, or phenyl; R¹⁶⁴, R¹⁶⁵,and R¹⁶⁶ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂₋₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; R¹⁶⁹, R¹⁷⁰, R¹⁷¹ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; and d is an integer from 1 to 10.

More preferred are compounds of the formula IIIa, IIIb and IIIc, even more preferred are compounds of the formula IIIa and IIIb, and most preferred are compounds of the formula IIIa. Preferably at least one of R¹, R², R^(1′), R^(2′), R^(1″) R^(2″), R^(1*), R^(2*) comprise a group E^(Si) and/or D^(Si).

More preferably R¹ and R² are the same, R^(1′) and R^(2′) are the same, R^(1″) and R^(1′) are the same, R^(1*) and R^(2*) are the same, wherein R¹, R², R^(1′), R^(2′), R^(1″) R^(2″), R^(1*) and R^(2*) contain a group E^(Si) and/or D^(Si).

Compounds of the formula

are more preferred,

R¹ and R² are selected from C₁-C₅₀alkyl, especially C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₁-C₅₀haloalkyl, especially C₁-C₂₅haloalkyalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₇-C₂₅arylalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₂-C₅₀alkenyl, especially C₂-C₂₅alkenyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₂-C₅₀alkinyl, especially C₂-C₂₅alkinyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₂-C₅₀haloalkenyl, especially haloalkenyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); C₅-C₁₂cycloalkyl; which is substituted one or more times with ES and/or interrupted one or more times with D^(Si); phenyl, or naphthyl which are substituted one or more times with E^(Si), a is 1, 2, or 3, a′ is 1, 2, or 3; wherein R¹⁰, D^(Si), E^(Si), Ar¹ and Ar^(1′) are as defined above. R^(10′) has the meaning of R¹⁰.

More preferred. R¹ and R² are C₁-C₂₅alkyl which is substituted one or more times with Es and/or interrupted one or more times with D^(Si); especially C₁-C₂₅alkyl which is substituted one or more times with EN, very especially C₁-C₈alkyl which is substituted one or more times with E^(Si).

Even more preferred, R¹ and R² are selected from C₁-C₂₅alkyl, which is substituted one or more times with Es and/or interrupted one or more times with D^(Si).

Most preferably R¹ and R² are C₁-C₈alkyl which is substituted with E^(Si). R¹ and R² may be different, but are preferably the same.

Ar¹ and Ar^(1′) may be different, but are preferably the same. Preferably, Ar¹ and Ar^(1′) are independently of each a group of formula XIa, XIb, XIc, XIe, XIf, XII, XIp, XIr, XIIs, XIx, XIIf, XIIg, XIIIa, XIIId, or XIIII. More preferably, Ar¹ and Ar′ are a group of formula XIa, XIb, XIe, XIf, XIr, XIx, or XIIIa. Still more preferably Ar¹ and Ar^(1′) are a group of formula XIa, XIb, or XIf. Most preferred Ar¹ and Ar^(1′) are a group of formula XIa, or XIf, especially XIa.

Among the compounds of formula IIIa compounds of formula

especially

especially

especially

very especially

especially

especially

are more preferred, wherein R¹⁰ and R^(10′) are as defined above, R¹ and R² may be the same or different and are selected from C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si); R³ and R^(3′) are independently of each other hydrogen, halogen, cyano or C₁-C₂₅alkyl, especially hydrogen or C₁-C₂₅alkyl; R⁷ and R^(7′) are independently of each other hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), more preferably C₄-C₂₅alkyl; R⁸ and R^(8′) are independently of each other hydrogen, C₁-C₂₅alkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; more preferably hydrogen, or C₁-C₂₅alkyl; and R¹² and R^(12′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or ≡R¹³, wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group.

R¹⁰ and R^(10′) are preferably H, F, trifluoromethyl, cyano, C₁-C₂₅alkyl, a group of formula

wherein R²⁴ to R²⁶ are as defined above and are preferably H, or C₁-C₂₅alkyl, more preferably H.

Among compounds of formula (IIa-1) to (IIIa-14) compounds are more preferred, wherein R¹ and R² may be the same or different and are selected from C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si);

R³ and R^(3′) are hydrogen or C₁-C₂₅alkyl; R⁷ and R^(7′) are C₄-C₂₅alkyl; R⁸ and R^(8′) are hydrogen, or C₁-C₂₅alkyl; R¹⁰ and R^(10″) are preferably H, F, trifluoromethyl, cyano, C₁-C₂₅alkyl, a group of formula

and R¹² and R¹⁷ are independently of each other hydrogen, cyano, C₁-C₂₅alkyl, or ≡R¹³, wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group.

Examples of specific compounds are shown below:

In another preferred embodiment the present invention is directed to compounds of formula

wherein R¹, R², A¹, A² and A³ are as defined above. R^(1′) and R²have independently of each other the meaning of R¹.

Preferably, A¹ and A² are independently of each other a group of formula

Preferably, A³ is a group of formula

R¹ and R² may be the same or different and are preferably selected from C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si). R^(1′) and R^(2′) may be the same or different and are preferably selected from C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si).

Examples of a compound of formula IIIb are shown below:

Compounds of the formula

(A³ is a group of formula, *Ar⁴_(k)Ar⁵_(l)Ar⁶_(r)Ar⁷^(z)-*, Ar⁴ is Ar⁷, k is 1, or 2, z is 1, or 2) may be prepared by reacting a compound of formula

with a compound of formula X^(16′)Ar⁵_(r)Ar⁶_(r)X^(16′), wherein X^(16′) is —B(OH)₂, —B(OH)₃—, —BF₃, —B(OY¹)₂,

and X¹⁶ is halogen, such as, for example, Br, or I.

The Suzuki reaction is typically conducted at about 0° C. to 180° C. in an aromatic hydrocarbon solvent such as toluene, xylene. Other solvents such as dimethytformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon. An aqueous base, preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scavenger. A condensation reaction may take 0.2 to 100 hours. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252.

In the above Suzuki coupling reactions the halogen X¹⁶ on the halogenated reaction partner can be replaced with the X^(16′) moiety and at the same time the X^(16′) moiety of the other reaction partner is replaced by X¹⁶.

In an additional embodiment the present invention is directed to compounds of formula A^(1″)-Y-A³-Y¹⁵A⁴-Y¹⁶_(p)A⁵-Y¹⁷_(q)A_(2″) (XX), wherein

A^(1″) and A^(2′) are independently of each other a group of formula Ar¹_(a)Ar²_(b)Ar³_(c)—X³, X³ is independently in each occurrence ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein two groups optionally form a common ring and these groups are branched or unbranched a X¹² is a halogen atom, very especially I, or Br; —OS(O)₂CF₃, —OS(O)₂-a, especially

OS(O)₂CH₃, —B(OH)₂, —B(OH)₃—, —BF₃—, —B(OY¹)₂,

where Y¹ is independently in each occurrence a C₁-C₁₂alkyl group and Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹—Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, ¹¹ and Y¹² are independently of each other hydrogen, or a C₁-C₁₂alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—, —CH₂C(CH₃)₂ CH₂—, and Y¹³ and Y¹⁴ are independently of each other hydrogen, or a C₁-C₁₂alkyl group; a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴ and A⁵ are as defined above.

The compound of formula XX is preferably a compound of formula A^(1″)-Y-A³-Y¹⁵-A^(2″) (XXa). The compounds of the formula XX, especially XXa are intermediates in the production of polymers.

Accordingly, the present invention is also directed to polymers comprising repeating units of formula -A^(1′)-Y-A³-Y¹⁵A⁴-Y¹⁶_(p)A⁵-Y¹⁵_(q)A²″-(X), wherein

A^(1′) and A^(2′) are independently of each other a group of formula Ar¹_(a)Ar²_(b)Ar³_(c)—, wherein a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴ and A⁵ are as defined above. The polymers of the present invention may be used in the production of semiconductor devices. Accordingly, the present invention is also directed to semiconductor devices comprising a polymer of the present invention.

Advantageously, the compound of formula III, or an organic semiconductor material, layer or component, comprising the compound of formula III can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).

A mixture containing the compound of formula III results in a semi-conducting layer comprising the compound of formula III (typically 0.1% to 99.9999% by weight, more specifically 1% to 99.9999% by weight, even more specifically 5% to 99.9999% by weight, especially 20 to 85% by weight) and at least another material. The other material can be, but is not restricted to another compound of formula III, a polymer of the present invention, a semiconducting polymer, a non-conductive polymer, organic small molecules, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles (Au, Ag etc.), insulator materials like the ones described for the gate dielectric (PET, PS etc.).

Accordingly, the present invention also relates to an organic semiconductor material, layer or component, comprising a compound of formula III and to a semiconductor device, comprising a compound of formula III and/or an organic semiconductor material, layer or component.

The semiconductor is preferably an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor. The structure and the components of the OFET device has been described in more detail above.

Accordingly, the invention provides organic photovoltaic (PV) devices (solar cells) comprising a compound of the formula III.

The structure of organic photovoltaic devices (solar cells) is, for example, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.

The PV device comprise in this order:

(a) a cathode (electrode), (b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (c) a photoactive layer, (d) optionally a smoothing layer, (e) an anode (electrode), (f) a substrate.

The photoactive layer comprises the compounds of the formula III. Preferably, the photoactive layer is made of a compound of the formula III, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor. As stated above, the photoactive layer may also contain a polymeric binder. The ratio of the small molecules of formula III to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA).

The fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C₆₀) and the related “spherical” fullerenes as well as carbon nanotubes. Fullerenes may be selected from those known in the art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₀ to C₉₆. Most preferably the fullerene is C₆₀ or C₇₀, such as [60]PCBM, or [70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics. The acceptor material can also be a material selected from the group consisting of another compounds of formula III, or any semi-conducting polymer, such as, for example, a polymer of formula I, provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a compound of the formula III, as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-Blodgett (“LB”) method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer. Instead of toluene, which is typical, a dispersion agent such as chlorobenzene is preferably used as a solvent. Among these methods, the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, the casting method and ink jet printing method, the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyttetrahydrofurane, N,N-dimethytformamide, acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum. Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006) and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order

(a) a cathode (electrode), (b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (c) a photoactive layer, (d) optionally a smoothing layer, (e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.) (f) optionally an extra electrode to match the energy level, (g) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride, (h) a photoactive layer, (i) optionally a smoothing layer, (j) an anode (electrode), (k) a substrate.

The PV device can also be processed on a fiber as described, for example, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or films comprising the compounds of the formula III can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US2003/0021913.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,     -   a drain electrode,     -   a gate electrode,     -   a semiconducting layer,     -   one or more gate insulator layers, and     -   optionally a substrate, wherein the semiconductor layer         comprises a compound of formula III.

The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a compound of formula III located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.

The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight. Weight-average molecular weight (Mw) and polydispersity (Mw/Mn=PD) are determined by Heat Temperature Gel Permeation Chromatography (HT-GPC) [Apparatus: GPC PL 220 from Polymer laboratories (Church Stretton, UK; now Varian) yielding the responses from refractive index (RI), Chromatographic conditions: Column: 3 “PLgel Olexis” column from Polymer Laboratories (Church Stretton, UK); with an average particle size of 13 im (dimensions 300×8 mm I.D.) Mobile phase: 1,2,4-trichlorobenzene purified by vacuum distillation and stabilised by butyihydroxytoluene (BHT, 200 mg/I), Chromatographic temperature: 150° C.; Mobile phase flow: 1 ml/min; Solute concentration: about 1 mg/ml; Injection volume: 200 11; Detection: RI, Procedure of molecular weight calibration: Relative calibration is done by use of a set of 10 polystyrene calibration standards obtained from Polymer Laboratories (Church Stretton, UK) spanning the molecular weight range from 1′930′000 Da - 5′050 Da, i. e., PS 1′930′000, PS 1′460′000, PS 1′075′000, PS 560′000, PS 330′000, PS 96′000, PS 52′000, PS 30′300, PS 10′100, PS 5′050 Da. A polynomic calibration is used to calculate the molecular weight.

All polymer structures given in the examples below are idealized representations of the polymer products obtained via the polymerization procedures described. If more than two components are copolymerized with each other sequences in the polymers can be either alternating or random depending on the polymerisation conditions.

EXAMPLES Example 1 Synthesis of Compound 6 (B−1)

a) 10 g of compound 1 [850583-75-4] and 18.43 g of potassium carbonate are dispersed in 100 ml of dry dimethytformamide. The mixture is heated to 100° C. for two hours and then 17.76 g of compound 2 [18135-48-3] are added and the reaction mixture is stirred for another hour at 100° C. The reaction mixture is cooled to room temperature and then poured on water. The product is extracted with chloroform. The organic phase is dried over MgSO₄ and the solvent is evaporated. The product is purified over silica gel by chromatography to give compound 3. ¹H-NMR data (ppm, CDCl₃): 8.96 2H d, 7.65 2H d, 7.31 2H dxd, 4.07 4H t, 1.81-1.70 4H m, 0.62 4H m, 0.01 18H s. 12 g of compound 3 and 7.99 g of N-bromosuccinimide (NBS) are added to 240 ml of chloroform. The mixture is cooled to −15° C. and then 0.074 g of 60% perchloric acid in water are added and the reaction mixture is stirred for 40 minutes at −15° C. Then the chloroform solution is washed with water, dried over MgSO₄ and then the solvent is evaporated. The product is recrystallized from dichloromethane and then from isopropanol to give a compound of formula 4. ¹H-NMR data (ppm, CDCl₃): 8.69 2H d, 7.24 2H d, 3.97 4H t, 1.76-1.65 4H m, 0.60 4H m, 0.01 18H s.

b) 1 g of compound 4, 0.89 g of compound 5 [479719-88-5], 0.8 mg of Pd(II)acetate and 4.9 mg of 2-(di-tert-butylphosphine)-1-phenylindole are added into a reactor under Argon. Then 12 ml of degassed tetrahydrofuran are added under argon and the mixture is heated to 60° C. Then 367 mg of lithiumhydroxide-monohydrate are added and the reaction mixture is heated for two hours under reflux. The mixture is poured on methanol and is filtered. The filter cake is then purified by chromatography over silica gel to give a compound of formula 6. ¹H-NMR data (ppm, CDCl₃): 8.97 2H d, 7.32 2H d, 7.28-7.22 6H m, 7.14 2H d, 7.06 2H dxd, 4.09 4H t, 1.88-1.72 4H m, 0.66 4H m, 0.03 18H s.

Example 2 Synthesis of Compound 11 (I-1)

a) 5 g of compound 1 [850583-75-4] and 7.04 g of potassium carbonate are dispersed in 50 ml of dry dimethytformamide. The mixture is heated to 65° C. and then 6.04 g of allylbromide 7 [106-95-6] are added and the reaction mixture is stirred over night at 65° C. The reaction mixture is cooled to room temperature and then poured on water. The product is extracted with dichloromethane. The organic phase is dried over MgSO₄ and the solvent is evaporated. The product is purified by recrystallization to give a compound of formula 8. ¹H-NMR data (ppm, CDCl₃): 8.80 2H d, 7.65 2H d, 7.27 2H dxd, 6.07-5.98 2H m, 5.25 2H s, 5.21 2H d, 4.77-4.75 4H m. Compound 8 and two equivalents of N-bromo-succinimide (NBS) are added to chloroform. The mixture is cooled to −15° C. and then a drop of 60% perchloric acid in water is added and the reaction mixture is stirred for 2 hours at −15° C. Then the chloroform solution is washed with water, dried over MgSO₄ and then the solvent is evaporated. The product is purified by recrystallization to give a compound of formula 9.

b) Compound 9 and two equivalents of 1,1,1,3,5,5,5-heptamethyttrisiloxane 10 are added to toluene. Then Karstedt catalyst is added and the mixture is stirred at 50° C. The solvent is evaporated under reduced pressure and the product is purified by chromatography over silica gel to give a compound of formula 11.

Alternatively compound 11 can be obtained from compound 12 by bromination with NBS.

Example 3 Synthesis of Compound 12 (B-3)

Compound 8 and two equivalents of 1,1,1,3,5,5,5-heptamethytrisiloxane 10 are added to toluene. Then Karstedt catalyst (compound of platinum(0) and divinyltetramethyldisiloxane) is added and the mixture is stirred at 50° C. The solvent is evaporated under reduced pressure and the product is purified by chromatography over silica gel to give a compound of formula 12. ¹H-NMR data (ppm, CDCl₃): 8.92 2H d, 7.62 2H d, 7.28 2H dxd, 4.06 4H t, 1.77 4H txt, 0.59 4H t, 0.07 36H s, 0.05 6H s.

Example 4 Synthesis of Compound 16 (I-6)

a) Compound 15 is synthesized in analogy to compound 9.

b) Compound 16 is synthesized in analogy to compound 11.

Alternatively compound 16 can be obtained from compound 17 by bromination with NBS.

Example 5 Synthesis of Compound 17 (B-5)

Compound 17 is synthesized in anlogy to compound 12.

Example 6 Synthesis of Polymer 19 (P-6)

Polymer 19 is obtained by reaction of compound 16 with one equivalent of compound 18 [145483-63-2] under Stille coupling reaction conditions.

Example 7 Synthesis of Polymer 26 (P-7)

a) Compound 22 is synthesized starting from compound 20 [88949-34-2] in analogy to compound 9 in Example 2.

b) Compound 24 is synthesized starting from compound 22 and compound 23 [2895-07-0] in analogy to compound 11 in Example 2.

c) Compound 26 is synthesized starting from compound 24 and compound 25 [476004-83-8] in analogy to compound 12 in Example 8 of WO2011/144566.

Example 8 Synthesis of Compound 31 (I-9)

a) Compound 28 is obtained from compound 1 and 8-bromo-1-octene 27 in analogy to compound 8 and is purified by column chromatography. ¹H-NMR data (ppm, CDCl₃): 8.93 2H d, 7.65 2H d, 7.30 2H dxd, 5.88-5.74 2H m, 5.04-4.92 4H m, 4.09 4H t, 2.05 4H txt, 1.75 4H txt, 1.44-1.22 12H m. b) Compound 29 is obtained from compound 28 in analogy to compound 9 and is purified by column chromatography. ¹H-NMR data (ppm, CDCb): 8.68 2H d, 7.26 2H d, 5.88-5.75 2H m, 5.05-4.93 4H m, 4.03 4H t, 2.05 4H txt, 1.72 4H txt, 1.46-1.27 12H m.

c) 3.6 g of compound 29 and 3.15 g of pentamethyldisiloxane 30 are added to 40 ml toluene under argon. Then 5 mmol Karstedt catalyst in toluene is added (20 drops) and the mixture is stirred at reflux ovemight. The solvent is evaporated under reduced pressure and the product is purified by chromatography over silica gel to give a compound of formula 31. 1H-NMR data (ppm, CDCb): 8.69 2H d, 7.25 2H d, 4.00 4H t, 1.74 4H txt, 1.50-1.25 20H m, 0.51 4H t, 0.07 18H s, 0.05 12H s.

Example 9 Synthesis of Compound 32 (I-8)

Compound 32 is obtained from compound 29 and 1,1,1,3,5,5,5-heptamethytrisiloxane 10 in analogy to compound 31.

Example 10 Synthesis of Polymer 34 (P-10)

400 mg of compound 31 and 137.8 mg of thiophene-diboronicacidpinacolester 33 are dissolved together with 3.7 mg palladium(II)acetate and 22.1 mg of 2-(di-tert-butylphosphino)-1-phenylindole[740815-37-6] in 25 ml of degassed tetrahydrofurane under argon. The whole mixture is refluxed for 30 minutes and then 103.2 mg of LiOH-monohydrate is added. The reaction mixture is then refluxed 1.5 hours under argon. The reaction mixture is poured on water, precipitated and filtered. The crude polymer is then dissolved in chloroform and the organic phase is refluxed together with a 1% water solution of NaCN during 1 hour. The phases are separated and the organic phase is still washed 3 times with water. Then the polymer is precipitated out of the chloroform solution with methanol. The crude polymer is then fractionated by Soxhlet extraction with heptane, tetrahydrofurane and chloroform. The chloroform fraction contained 230 mg of the desired polymer. Mw 7′900, polydispersity 1.17 (measured by high temperature GPC at 150° C. with trichlorobenzene).

Example 11 Synthesis of Polymer 35 (P-8)

Compound 35 is obtained from compound 32 and compound 33 in analogy to compound 34.

Example 12 Synthesis of Compound 36 (B-20)

Compound 36 is obtained in analogy to compound 12 from compound 8 and pentamethyldisiloxane 30. ¹H-NMR data (ppm, CDCb): ¹H-NMR data (ppm, CDCb): 8.93 2H d, 7.64 2H d, 7.30 2H dxd, 4.08 4H t, 1.79 4H txt, 0.63 4H t, 0.09 18H s, 0.07 12H s.

Example 13 Synthesis of Compound 37 (I-10)

1 g of compound 36 is dissolved in 10 ml of chloroform. Then 550 mg of N-bromosuccinimid (NBS) are added and the reaction mixture is stirred at room temperature ovemight. The solvent is evaporated under reduced pressure and the product is chromatographed over silica gel to get compound 37. ¹H-NMR data (ppm, CDCl₃): ¹H-NMR data (ppm, CDCl₃): 8.69 2H d, 7.26 2H d, 3.98 4H t, 1.75 4H txt, 0.63 4H t, 0.09 18H s, 0.07 12H s;

Example 14 Synthesis of Compound 41 (B-18)

a) Compound 39 is obtained from compound 1 and bromo-methyl-trimethylsilane 38 in analogy to compound 3. ¹H-NMR data (ppm, CDCb): 8.88 2H d, 7.62 2H d, 7.30 2H dxd, 3.76 4H s, 0.09 18H s. b) Compound 40 is obtained from compound 39 in analogy to compound 4. ¹H-NMR data (ppm, CDCb): 8.64 2H d, 7.25 2H d, 3.64 4H s, 0.11 18H s.

c) Compound 41 is obtained from compound 40 and [479719-88-5]5 in analogy to compound 6. ¹H-NMR data (ppm, CDCb): 8.93 2H d, 7.33 2H d, 7.31-7.24 6H m, 7.15 2H d, 7.07 2H dxd, 3.78 4H s, 0.15 18H s.

Example 15 Synthesis of Compound 45 (B-21)

a) Compound 43 is obtained from compound 1 and bromo-methyl-trimethysilane 42 in analogy to compound 3. ¹H-NMR data (ppm, CDCl₃): 8.74 2H d, 7.72 2H d, 7.31 2H dxd, 4.86 4H s, 0.11 18H s.

b) Compound 44 is obtained from compound 43 in analogy to compound 4. ¹H-NMR data (ppm, CDCl₃): 8.46 2H d, 7.25 2H d, 4.77 4H s, 0.13 18H s.

c) Compound 45 is obtained from compound 44 and [479719-88-5]5 in analogy to compound 6. ¹H-NMR data (ppm, CDCl₃): 8.73 2H d, 7.34 2H d, 7.31-7.24 6H m, 7.16 2H d, 7.09 2H dxd, 4.88 4H s, 0.15 18H s.

Application Example 1 Application of the Semiconducting Compound 6

The semiconductor thin film is prepared by spin-coating the compound of the formula 6 obtained in example 1 in a 0.5% (w/w) solution in chloroform. The spin coating is accomplished at a spinning speed of 3000 rpm (rounds per minute) for about 20 seconds in ambient conditions. The devices are evaluated as deposited and after being annealed at 100° C. for 15 minutes.

Transistor Performance

The transistor behavior is measured on an automated transistor prober (TP-10, CSEM Zü-rich) and showed clear transistor behavior.

Application Example 2 Photovoltaic Application of the Semiconducting Compound 6

The solar cell has the following structure: Al electrode/LiF layer/organic layer, including compound of the invention/[poly(3,4-ethylenedioxy-thiophene) (PEDOT)/poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate. The solar cells are made by spin coating a layer of the PEDOT-PSS on a pre-patterned ITO on glass substrate. Then a 1:1 mixture of the compound of formula 6 (1% by weight): [70]PCBM (a substituted C₇₀ fullerene) is spin coated (organic layer). LiF and Al are sublimed under high vacuum through a shadow-mask.

Solar Cell Performance

The solar cell is measured under a solar light simulator. Then with the External Quantum Efficiency (EQE) graph the current is estimated under AM1.5 conditions.

Application Example 1 (Bottom-Gate Bottom Contact (BGBC) Field Effect Transistor (FET)) Semiconductor Film Deposition

Siliconwafers (Si n−(425±40 μm)) with a 230 nm thick SiO₂ dielectric and patterned indium tin oxide (15 nm)/ gold (30 nm) contacts (L=20, 10, 5, 2.5 μm, W=0.01 m; Fraunhofer IPMS (Dresden)) are prepared by standard cleaning by washing with acetone and i-propanol followed by oxygen plasma treatment for 30 minutes.

The substrates are transferred in a glove box. An octyltrichlorsilane (OTS) monolayer is grown on the dielectric surface by putting the substrates in a 50 mM solution of octyitri-chlorosilane (OTS) in trichloroethylene for 1 h. After monolayer growth, the substrates are washed with toluene to remove physisorbed silane.

The semiconductor P-10 is dissolved in CHCb in a concentration 0.75% by weight at 80° C. and spin-coated at 1500 rpms for 60 s onto the substrates.

Application Example 4 Top Gate Bottom Contact (TGBC) FET

Substrate preparation: For TGBC FETs PET substrates with lithographically patterned 50 nm gold (Au) contacts covered with photoresist are used. Substrates are prepared by standard cleaning in acetone and ethanol and dried at 60° C. for 30 min.

Transistor preparation: The semiconductor P-10 is dissolved in trichloroethylene (0.75 wt %) at 80° C. for 4 h., filtered through a 0.45 pJ filter, spun to achieve a 50 nm layer and dried for 30 s at 80° C. Immediately after 500 nm layer of dielectric (CYTOP) has been spin-coated and dried for 2 minutes at 80° C. 120 nm gold is evaporated through a shadow mask as gate contact.

BGBC and TGBC OFET Measurement: OFET transfer and output characteristics are measured on an Agilent 4155C semiconductor parameter analyzer. The devices are annealed in a glovebox at 150° C. for 15 minutes before the measurements are done in a glove box under a nitrogen atmosphere at room temperature. For p-type transistors the gate voltage (Vg) varies from 10 to −30 V and at drain voltage (V_(d)) equal to −3 and −30V for the transfer characterisation. For the output characterization V_(d) is varied from 0 to −30V at V₉=0, −10, −20, −30 V.

The results of BGBC and TGBC FET measurements are reported in the Table below:

Appl. Semi- Mobility, Example conductor Solvent cm²/Vs On/off 3 P-10 CHCl₃ 1.40E−01 3.80E+06 4 P-10 CH₃CCl₃ 0.11 3.00E+04 

1: A polymer comprising a repeating unit of the formula

wherein a is 0, 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or 3; c is O, 1, 2, or 3; c′ is 0, 1, 2, or 3; R¹ and R² may be the same or different and are selected from the group consisting of a C₁-C₁₀₀alkyl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si), a C₂-C₁₀₀alkenyl group, which can optionally be substituted one or more times with C₁-C₁₂ alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si), a C₃-C₁₀₀alkinyl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si), a C₃-C₁₂cycloalkyl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si), a C₆-C₂₄aryl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); a C₂-C₂₀heteroaryl group, which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂alkoxy, halogen, C₅-C₁₂cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and —CO—C—C₁₈alkyl, —CO—C₅-C₁₂cycloalkyl, —COO—C₁-C₁₈alkyl which can optionally be substituted one or more times with C₁-C₁₂alkyl, C₁-C₁₂ alkoxy, halogen, C₅-C₁₂ cycloalkyl, nitro, cyano, vinyl, allyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, or E^(Si); and/or can optionally be interrupted by —O—, —S—, —NR³⁹—, —COO—, —CO—, —OCO—, C₆-C₂₄arylene, C₂-C₂₀heteroarylene, C₃-C₁₂cycloalkylene, or D^(Si): wherein E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³ or —O—SiR¹⁶¹R¹⁶²R¹⁶³, D^(Si) is —SiR¹⁶¹R¹⁶²—, —SiR¹⁶¹R¹⁶²—(O—SiRi¹⁶¹R¹⁶²)_(d)— or —O—SiR¹⁶¹R¹⁶²—. R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl, C₁-C₂₅ haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁷R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy; R¹⁶⁴, R¹⁶⁵ and R¹⁶⁶ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂ cycloalkyl, which might optionally be substituted with C₁-C₄alkyl, C₁-C₂haloalkyl, C₂-C₂₅alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, C₁-C₂₅ alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy; R¹⁶⁹, R¹⁷⁰ and R¹⁷¹ are independently of each other hydrogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, which might optionally be substituted with C₁-C₄alkyl, C₁-C₂₅haloalkyl, C₂-C₂₅alkenyl, —O—Si(CH₃)₃, C₁-C₂₅alkoxy, C₃-C₂₄(hetero)aryloxy, NR¹⁶⁷R¹⁶⁸, halogen, C₁-C₂₅acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C₁-C₂₄alkyl, halogen, cyano or C₁-C₂₅alkoxy; R¹⁶⁷ and R¹⁶⁸ are independently of each other hydrogen, C₆-C₁₈ aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C₇-C₂₅arylalkyl; d is an integer from 1 to 50; R³⁹ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈haloalkyl, C₇-C₂₅arylalkyl, or C₁-C₁₈alkanoyl, Ar¹, Ar^(1′) Ar², Ar^(2′), Ar³ and Ar³′ are independently of each other

wherein X is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′)), —Ge(R)(R^(11′))—, —C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are independently of each other hydrogen, halogen, E^(Si), halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C₇-C₂₅arylalkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₁-C₂₅alkoxy; R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) are independently of each other hydrogen, halogen, E^(Si), halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C₁-C₂₅arylalkyl, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₁-C₂₅alkoxy; R⁷, R^(7′), R⁹ and R^(9′) are independently of each other hydrogen, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₇-C₂₅arylalkyl, or R⁷ and R^(7′), or R⁹ and R^(9′) are together ═CR¹⁰⁴R^(104′); R⁸ and R^(8′) are independently of each other hydrogen, C₆-C₁₈aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C₁-C₂₅alkyl substituted with one or more E^(Si), or C₇-C₂₅arylalkyl, R¹¹ and R^(11′) are independently of each other C₁-C₂₅alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or ≡R¹³, wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; Ar¹, Ar^(1′), Ar², Ar^(2′), A³ and A^(3′) are independently of each other

wherein X^(1′) is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′)), —C(R¹⁰⁸)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano, COOR¹⁰³, a C₁-C₂₅alkyl group, a C₆-C₂₄aryl or C₂-C₂₀heteroaryl; R¹⁰³ is C₁-C₂₅alkyl, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or is C₇-C₂₅arylalkyl; R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C₇-C₂₅arylalkyl, or C₁-C₁₈alkoxy, R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, C₁-C₁₈perfluoroalkyl, C₁-C₂₅alkyl, which may be interrupted by —O—, or —S—; or —COOR¹⁰³; R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted by D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁸ and R¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, wherein R¹¹⁰ and R¹¹¹ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or R¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, which optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, D is —CO—, —COO—, —S—, —O—, or —NR¹¹²—, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, or halogen, G is E, or C₁-C₁₈alkyl, and R¹¹² and R¹¹³ are independently of each other H, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl or C₁-C₁₈alkoxy, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—, R¹¹⁴ is C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or ≡R¹¹⁶, wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are independently of each other hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R¹²² and R^(122′) are independently of each other hydrogen, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C₇-C₂₅arylalkyl, with the proviso that at least one of the groups R¹, R², R³, R^(3′), R⁴, R^(4′), R⁵, R^(5′), R⁶, R^(6′), R⁷, R^(7′), R⁸, R^(8′), R⁹ and R^(9′) comprise E^(Si) and/or D^(Si). 2: The polymer according to claim 1, which is a polymer comprising a repeating unit of the formula

wherein R¹ and R² may be the same or different and are selected from C₁-C₂₅alkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si), C₁-C₂₅haloalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si), C₇-C₂₅arylalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si), C₂-C₂₅alkenyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si), C₂-C₂₅haloalkenyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si), C₅-C₁₂ cycloalkyl, which is substituted one or more times with E^(Si) and/or interrupted one or more times with D^(Si), phenyl, or naphthyl which are substituted one or more times with E^(Si), and a is 1, 2, or 3, a′ is 1, 2, or
 3. 3: The polymer according to claim 1, comprising at least one unit of the formula Ia to Ie,

wherein R¹ and R² may be the same or different and are selected from C₁-C₈alkyl which is substituted with E^(Si), E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³; R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₈alkyl, C₅-C₆cycloalkyl, which might optionally be substituted with C₁-C₄alkyl, C₁-C₈haloalkyl, C₂- C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, or phenyl; R¹⁶⁴, R¹⁶⁵, R¹⁶⁶ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; R¹⁶⁹, R¹⁷⁰, R¹⁷¹ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; d is an integer from 1 to 10; R³ and R^(3′) are independently of each other hydrogen, or C₁-C₂₅alkyl; and R⁸ and R^(8′) are independently of each other hydrogen, or C₁-C₂₅alkyl. 4: The polymer according to claim 1, comprising one or more unit and/or one or more repeating unit of the formula *A* and *COM¹*, wherein A is a repeating unit of formula (I), and —COM¹- is a repeating unit Ar² where Ar² is as defined in claim 1, or is a group of formula *Ar¹⁴^(s)Ar¹⁵_(t)Ar¹⁶_(u)Ar¹⁷_(v)* s is 1, t is 1, u is 0or 1, v is 0or 1, and Ar¹⁴, Ar¹⁵, Ar¹⁶ and Ar¹⁷ are independently of each other a group of formula

wherein one of X⁵ and X⁶ is N and the other is CR¹⁴, and R¹⁴, R^(14′), R¹⁷ and R^(17′) are independently of each other H or a C₁-C₂₅alkyl group. 5: The polymer according to claim 4, wherein A is a repeating unit of formula (Ia), (Ib), or (Id),

and *COM¹* is a group of formula,

where R³, R^(3′), R¹⁴ and R^(14′) are independently of each other hydrogen or C₁-C₂₅alkyl, and R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano or a C₁-C₂₅alkyl group. 6: The polymer according to claim 4, which is a polymer of the formula Ia1 to Ia7,

wherein n is from 4 to 1000, R¹ and R² may be the same or different and are a C₁-C₈alkyl which is substituted with E^(Si), R³ and R^(3′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy; E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³; R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₈alkyl, C₅-C₆cycloalkyl, which might optionally be substituted with C₁-C₄alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, or phenyl; R¹⁶⁹, R¹⁶⁵ and R¹⁶⁶ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰)_(d)—R¹⁷¹, or phenyl; R¹⁶⁹, R¹⁷⁰ and R¹⁷¹ are independently of each other C₁-C₈alkyl, C₁-C₂haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; d is an integer from 1 to 10; R^(3″) and R^(3*) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy; R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano, COOR¹⁰³, C₁-C₂₅alkyl, wherein R¹⁰³ is C₁-C₈alkyl; and R¹⁰⁵ and R^(105′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl or C₁-C₂₅alkoxy. 7: A compound of the formula A¹-YA³-Y¹⁵_(o)A⁴-Y¹⁶pA⁵-Y¹⁷_(q)-A²(III), wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group of formula

o is 0 or 1, p is 0 or 1, q is 0 or 1; A¹ and A² are independently of each other a group of formula Ar¹_(a)Ar²_(b)Ar³_(c)—R¹⁰, A³, A⁴ and A⁵ are independently of each other a group of formula Ar⁴_(k)Ar⁵_(l)Ar⁶_(r)Ar⁷_(z)* k is 0, 1, 2, or 3; 1 is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1,2, or 3; R¹⁰ is hydrogen, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted one or more times by E and/or interrupted one or more times by D, E^(Si), C₁-C₂₅alkyl which is substituted one or more times by E^(Si) and/or interrupted one or more times by D^(Si),

COO—C₁-C₁₈alkyl, C₄-C₁₈cycloalkyl group, C₄-C₁₈cycloalkyl group, which is substituted by G, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈ thioalkoxy, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl, which is substituted by G, or a group of formulae IVa to IVm,

wherein R²² to R²⁶ and R²⁹ to R⁵⁸ represent independently of each other H, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀ heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, a C₄-C₁₈cycloalkyl group, a C₄-C₁₈cycloalkyl group, which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl, which is substituted by G, R²⁷ and R²⁸ are independently of each other hydrogen, C₁-C₂₅alkyl, halogen, cyano or C₇-C₂₅aralkyl, or R²⁷ and R²⁸ together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, R⁵⁹ is hydrogen, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C₇-C₂₅arylalkyl, D is —CO—, —COO—, —S—, —O—, or —NR¹¹²—, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR¹¹²R¹¹³, —CONR¹¹²R¹¹³, or halogen, G is E, or C₁-C₁₈alkyl, and R¹¹² and R¹¹³ are independently of each other H, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl or C₁-C₁₈alkoxy, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—; R¹⁷² is hydrogen, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C₇-C₂₅arylalkyl; R²¹⁴ and R²¹⁵ are independently of each other hydrogen, C₁-C₁₈alkyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CN or COOR²¹⁶; R²¹⁶ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl or C₂-C₂₀heteroaryl; Ar⁴, Ar⁵, Ar⁶ and Ar⁷ have independently of each other the meaning of Ar¹, and a, b, c, D^(Si), E^(Si), Ar¹, Ar², Ar³, R¹ and R² are as defined in claim 1; with the proviso that at least one of the groups R¹, R², R³, R^(3′), R⁴, R^(4′), R⁵, R^(5′), R⁶, R^(6′), R⁷, R^(7′), R⁸, R^(8′), R⁹ and R^(9′) contains a group E^(Si) and/or D^(Si). 8: The compound according to claim 7, which is a compound of the formula IIIa to IIId,

wherein R¹, R², A¹, A², A³, A⁴ and As are as defined in claim 7, R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) have independently of each other the meaning of R¹, with the proviso that at least one of the groups R¹, R², R^(1′), R^(2′), R^(1″), R^(2″), R^(1*) and R^(2*) is a C₁-C₈alkyl group which is substituted with E^(Si), and E^(Si) is —SiR¹⁶¹R¹⁶²R¹⁶³; R¹⁶¹, R¹⁶² and R¹⁶³ are independently of each other C₁-C₈alkyl, C₅-C₆cycloalkyl which is optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁴R¹⁶⁵R¹⁶⁶, —(O—SiR¹⁶⁴R¹⁶⁵)_(d)—R¹⁶⁶, or phenyl; R¹⁶⁴, R¹⁶⁵, R¹⁶⁶ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—SiR¹⁶⁹R¹⁷⁰R¹⁷¹, —(O—SiR¹⁶⁹R¹⁷⁰ T)_(d)—R¹⁷¹, or phenyl; R¹⁶⁹, R¹⁷⁰, R¹⁷¹ are independently of each other C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, —O—Si(CH₃)₃, or phenyl; and d is an integer from 1 to
 10. 9: An organic semiconductor material, layer or component, comprising the polymer according to claim
 1. 10: An electronic device, comprising the polymer according to claim
 1. 11: The electronic device according to claim 10, wherein said device is an organic photovoltaic device, a photodiode, or an organic field effect transistor. 12: A method for the preparation of an electronic device, said method comprises applying a solution and/or dispersion of the polymer according to claim 1 in an organic solvent to a suitable substrate, and removing the solvent.
 13. (canceled) 14: A compound of the formula

wherein R¹, R², a, a′, b, b′, c, c′, Ar¹, Ar^(1′), Ar², Ar^(2′), Ar³ and Ar^(3′) are as defined in claim 1, X² and X^(2′) are independently of each other halogen, ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein two groups optionally form a common ring and these groups are branched or unbranched, X¹² is a halogen atom, or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group, and Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰- CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen or a C₁-C₁₀alkyl group, and Y¹³ and Y¹⁴ are independently of each other hydrogen or a C₁-C₁₀alkyl group. 15: A method for the preparation of a polymer of formula II, comprising reacting a dihalogenide of formula X¹⁰-A-X¹⁰ with an equimolar amount of a diboronic acid or diboronate corresponding to formula X¹¹COM¹X¹¹, in a solvent and in the presence of a catalyst, or reacting a dihalogenide of formula X¹⁰COM¹X¹⁰ with an equimolar amount of a diboronic acid or diboronate corresponding to formula X¹¹-A-X¹¹ in a solvent and in the presence of a catalyst, wherein X¹⁰ is halogen, and X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group, Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁷Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰- CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen or a C₁-C₁₀alkyl group, and Y¹³ and Y¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkyl group; or reacting a dihalogenide of formula X¹⁰-A-X¹⁰ with an equimolar amount of an organo tin compound corresponding to formula X^(11′)COM¹X^(11′), or reacting a dihalogenide of formula X¹⁰COM¹X¹⁰ with an equimolar amount of an organo tin compound corresponding to formula X^(11′)-A-X^(11′), wherein X^(11′) is independently in each occurrence —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl, or two of the groups R²⁰⁷, R²⁰⁸ and R²⁰⁹ form a ring and these groups are branched, or unbranched; A and COM¹ are as defined in claim
 4. 16: A polymer, comprising a repeating unit of formula -A^(1′)—Y-A³-Y¹⁵A⁴-Y¹⁶_(p)A⁵-Y¹⁷_(q)-A^(2′)—(X), wherein A^(1′) and A^(2′) are independently of each other a group of formula Ar¹_(a)Ar²_(b)Ar³_(c), and a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴ and A⁵ are as defined in claim
 7. 17: An organic semiconductor material, layer or component, comprising a compound according to claim
 7. 18: An electronic device, comprising a compound according to claim
 7. 19: An electronic device, comprising an organic semiconductor material, layer or component according to claim
 9. 20: A method for the preparation of an electronic device, said method comprises applying a solution and/or dispersion of a compound according to claim 7 in an organic solvent to a suitable substrate, and removing the solvent or optionally evaporating said compound. 